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Патент USA US2029317

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‘ Feb. 4, 1936.
Filed March '19, 1952
0 O
V 2 Sheets-Sheet 1
Patented Feb. 4, 1936
Jesse A. Guyer, Frederick E. Frey, and Walter F.
Huppke, Bartlesville, Okla, assignors to Phil
lips Petroleum Company, Bartlesville, 0kla., a
corporation of Delaware
Application March 19, 1932, Serial No. 600,017
2 Claims.
This invention relates to an apparatus to be
used with a process for the catalytic conversion of
hydrocarbon fluids into fuel gas by reacting a
hydrocarbon with steam in the presence of a cata
lyst at elevated temperatures.
A normal city gas plant in order to care for
the peak load demand would have to be designed
to carry a larger amount of gas than would be
necessary for the ordinary demand. By employ
1 (l ing this process in conjunction with a city gas
plant, it is not necessary to design the regular
plant to care for the peak load demand. A small
er out?t running economically at full rated ca
pacity throughout the day will care for the or
dinary load; any greater demand on the system
can easily be cared for by the catalytic conversion
of hydrocarbon gases. These gases may be stored
as liquids under a very small pressure, thereby
insuring the city plant against contingencies.
It is therefore an object of this invention to
provide an improved apparatus for the conm'ier
cially practical manufacture of fuel gas from hy
drocarbon fluids.
A further object of the invention is to furnish
25 an apparatus to manufacture a fuel gas by pass
ing a limited amount of steam, together with a
hydrocarbon ?uid through a catalytic chamber
or chambers of restricted volume.
Another object ofv this invention is to supply
30 equipment to control all conditions under which
this reaction is conducted, whereby it is possible
to produce a gas having predetermined charac
teristics of thermal value and density.
(01. 48--94)
cases, temperatures higher than are necessary
to obtain the catalytic reaction are used to pro
duce a gas substantially free from hydrocarbons.
We have found that if, in the manufacture of
fuel gas, higher ?ow rates and lower steam ratios
than hitherto used are employed, then well known
catalysts of the Fe group activated with di?icultly
reducible oxides of Al, Cr, V, etc., can be used to
commercial and practical advantages. The proc
ess may be applied more advantageously to the
higher hydrocarbons of the paraffin type such as
propane and butane, but gases containing a large
proportion of the comparatively unreactive meth
ane, as well as gases produced by cracking, which
contain the simpler ole?nes, may be treated suc 15
cessfully by the process. We can also use liquid
hydrocarbons which can be completely vaporized.
Under conditions Where speci?c proportions of
hydrocarbons are reacted with speci?c propor
tions of steam at an elevated temperature pref 20
erably above 600° C. in the presence of certain
catalysts, the operation can be so controlled that
portions of the hydrocarbons remain unreacted so
that fuel gas of a desired thermal value and
density can be produced.
The complete conversion of hydrocarbons into
oxides of carbon and hydrogen yields a gas with
a calori?c value of no more than 325 B. t. u. per
cubic foot. Since a calori?c value in excess of
500 B. t. u. per cubic foot is usually desired in 30
a fuel gas it is desirable that some of the hydro
carbons pass through the catalytic chamber or
chambers without conversion into water gas. In
A still further object is to provide an appa
ratus to react steam, in such a proportion to the
hydrocarbon gas as to produce substantially no
the past, such catalysts as nickel, iron, and cobalt
have been employed in the conversion of hydro
carbonization, thereby eliminating the difficulties
of pipes clogging and inactivity of the catalysts.
ing gas of lower calori?c value. When employed
in this manner, carbon deposits are formed.
Carbon formations can be tolerated in known
methods in which a catalyst is supported on heat
storing material disposed in a chamber into which
heating gases and reactants are alternately intro
duced for alternate heating and gas making
cycles, since restricted passages, subject to stop
page by carbon, are unnecessary. But in meth
ods of this type, wide variations in temperatures
during the gas making cycle are unavoidable and
great fluctuations in the properties of the gas
Another object is to provide an apparatus of
4 0 this kind, having a number of catalyst chambers
arranged in parallel relation, through which the
mixture of steam and hydrocarbons ?ows, the
catalyst being exposed in units su?iciently ex
tended to permit the introduction of the heat re
45 quired by the reaction through the con?ning wall
adjacent to the catalytic body.
A further object of the invention is to provide
an apparatus by which the process may be carried
out in a practical manner.
Water gas, composed of oxides of carbon and
hydrogen, is commonly prepared in a state of
comparative purity for use in catalytic synthesis
by the interaction of hydrocarbons with steam in
the presence of a suitable catalyst.
A large ex
55 cess of steam, moderate flow rate, and, in most
carbons, without steam, into hydrogen-contain
produced take place unless complete destruction
of the hydrocarbons is intended. For producing
a gas of uniform properties, a continuous proc
ess is desirable, but neither can partial combus
tion be used to avoid carbon, nor complete con
version into water gas be used economically, to
produce a gas. having a low speci?c gravity and.
at the same time an adjustable calori?c value in
the desired range.
In the case where a gas of higher calori?c value
is desired, then certain portions of the hydrocar
bons must remain unreacted. In order to control
these conditions, restricted passages and cata
lytic chambers of restricted volume must be em
ployed.» Carbon deposits formed would tend to
clog these passages and inactivate the catalysts.
We have found that by introducing limited
amounts of steam into the reaction, the forma
tion of carbon may be prevented, even while some
of the hydrocarbons still escape the water gas
conversion. This will continuously produce gases
15 of desired predetermined calori?c value. The
amount of steam may vary depending on the
properties of resulting gas desired. Less than one.
atom of oxygen in the form of water for each
atom of carbon in the hydrocarbon may ‘be used
20 and still prevent the formation of carbon de
With the foregoing objects outlined and with
other objects in view which will appear as the de
scription proceeds, the invention consists in the
25 novel features hereinafter described in detail,
illustrated in the accompanying drawings, and
more particularly pointed out in the appended
In the accompanying drawings,
Fig. 1 is a vertical section, partly in elevation
and more or less diagrammatical, of an appa
ratus for carrying out the process.
‘2 is ‘a ‘horizontal'section of Fig. 1, taken
_ on the line 2-—-2.
Fig. 3 is a view similar to Fig. 2, but illustrating
an alternative method of installing the catalyst.
The apparatus preferably comprises a housing
3 of heat insulating material divided by a baffle
plate 9a of similar material, into upper and lower
40 chambers ‘which are in communication with one
If air is to be mixed with the hydrocarbon ?uid
before the latter is introduced into the preheater
A, said air may be introduced through a valved
branch F of the inlet pipe I4.
At the point A’, the preheated hydrocarbon
?uid, with or Without admixture of air, is ad
mixed with the steam from the super-heater 8.
If too much steam for reaction with the hy
drocarbons is produced by the waste heat, some of
the steam may be discharged through a valved
pipe 12a, or if desired, for reducing the amount
of heat imparted to the boiler, some of the hot
v?nished gas, instead of passing directly through
the boiler I I, may be by-passed through a valved
passageway N before it is introduced into the 15
pipe G.
For the purpose of diluting the ?nished gas with
flue gas, a valved pipe I‘! connects the ?ue H]
with the pipe G, and a pump Ila is interposed
in this conduit for forcing the ?ue gas into the 20
pipe G.
Another valved pipe 16 is connectedto the pipe
G for use in introducing an enriching ?uid, such
as hydrocarbons, into the ?nished gas line.
A valved conduit i5 leads into the manifold D 25
between the catalyst tubes and the chamber D’
for the purpose of introducing a hydrocarbon en
riching ?uid into the hot fuel gas before the latter
is cooled by imparting some of its heat to the
boiler H. In this way, the enriching ?uid may 30
be cracked somewhat by the heat of the hot fuel
gas leaving the catalyst tubes.
'The catalyst in the tubes C’, C2, C3 and C4
preferably consists of wire screens of any suit
able cross section. For instance, each screen may 35
be of substantially the same length as the tube
within which it is placed, and may be M-shaped
in cross section. Such screens may be of nickel,
made active by oxidizing and then reducing to
produce a roughened condition. Afterwards, the 40
another at ‘one end only of the housing. At the screen is coated with a solution of a nickel and
opposite 'end of the housing, a suitable burner 4 aluminum nitrates, which, when dried and heated,
extends into the lower chamber. That chamber results in the formation of a catalytic nickel pro
is divided into upper and lower compartments by moted by alumina upon subsequent treatment
with a-heated hydrocarbon atmosphere.
45 a horizontal plate 4a of heat conducting material.
Thecompartment below the baffle 4a is the com
In starting the process, the boiler H may be
bustion chamber of the apparatus, and it is pro
heated by a burner H, and at such, time as it is
vided at one end with a perforated wall "6 through desirable to pass the combustion gases fromcham
whichgases of combustion travel to a passageway ber D’ into the stack H], such chamber is connect
50 ‘I, that conducts the same into the upper cham I ed by a passageway M with such stack, suitable
ber ‘of the apparatus. In the latter chamber, a dampers G’ and G2 being arranged respectively
. steam preheater or super-heater 8, and an air
in the pipe G and in the passagewayM.
preheater 9, are positioned in serial arrangement.
Instead of employing catalyst tubes of the type
After'the combustion gases pass through the up
shown in Figs. 1 and 2, we can use a single tube
55 per chamber, they are discharged through the
with catalytic ‘chambers interposed therein in
?ue or stack I0.
spaced relation, as shown in Fig. 3. In this ar
The air preheated in 9 is fed by a conduit 9b rangement, the single tube will be positioned be
into the combustion chamber.
low the baffle 9a, and at substantially the same
A waste heat boiler ll, positioned at one end elevation as the catalytic tubes in Figs. 1 and 2.
to of the housing, is ‘provided with an outlet conduit Referring to Fig. 3, it will be noted that the hy
drocarbon ?uid introduced through the pipe i4
l2 having a control valve E. This conduit dis
charges steam into the preheater or super
may be mixed with (air from the branch F before
entering the preheater A. As in Figs. 1 and 2,
heater 8.
steam from the preheater 8 is mixed with the
The hydrocarbon ?uid to be treated is intro
65 duced through a conduit I4, connected to a pre
hydrocarbons or hydrocarbons and air at the
heater A, arranged in the passageway l and dis
point A’, and thenthe mixture enters the cata
charging 'at A’ into a manifold B. This manifold, lyst tube 0. This tube is made up of a number
as ‘best shown in Fig. 2, communicates with a of cross pipes B’, B2, B3, B13, B5, which lead to
series of catalyst tubes C’, C2, C3, C4 that extend and from catalyst chambers C’, C2,'C3, C4, C5,
beneath the ba?ie 9a and above the plate 4a.
and C6. Each of these-chambers preferably con
tains a-catalyst composed of metals of the iron
A manifold D receives the gases from the cata
lyst tubes and conducts the same through conduit group activated with dif?culty reducible metal
E’ into a chamber D’ in which the waste heat lic oxides. For example, it may be nickel acti
boiler H is ‘arranged.
‘T on
The fuel gas or ?nished I vated with an alumina.
gas is ‘discharged through a-‘pipe 'G.
The ‘catalyst may-also be of pumice or porce
lain crushed and screened from 3 to 6 mesh to
the inch size, and impregnated with nickel and
aluminum nitrates which are decomposed by cal
cination at low red heat to give the oxides. For
(If the purpose of holding such a catalyst in position,
a perforated alloy plate is spot welded into place
at one end of the chamber. Afterwards, the cata
lyst is put in and held in place by a second per
forated alloy plate.
In order that the catalyst chambers may be
accessible, openings are placed in the opposite
walls of the housing 3 where the catalyst cham
bers are located, and these openings are normally
closed by any suitable doors 25.
As in Figs. 1 and 2, the fuel gas leaving the last
one of the catalyst chambers CS, enters a pipe D
which conducts the same to the boiler l I, (Fig. 1).
If desired, hydrocarbon ?uid, with or without
admixture with air, can be fed by way of pipes J
20 and valved branch pipes J ’, J2, J3, J4 and J5, into
the inlet ends of the catalyst chambers.
If the catalyst sections are arranged along the
walls of the housing, the small pipes J’, J 2, J 3, J 4
and J5 for the addition of hydrocarbons progres
sively in small portions, may be run through the
furnace in such a way that they would not be
exposed to excessive temperatures so that undue
cracking is prevented.
In putting the apparatus in operation, steam is
?rst generated by heating boiler II by the com
bustion of fuel gas in the chamber D’. Air for
combustion here is admitted through gate con
trolled opening K, and the products of combus
tion are allowed to pass through the boiler tubes
and into the stack l0 through opening M, while
the valved pipe G remains closed to prevent the
passage of combustion gases into the fuel gas
When the catalyst tubes have been heated
somewhat by firing combustion chamber 5, steam
is admitted to said tubes by opening valve E, ?r
ing through burner H is discontinued, gate K
and damper G2 are closed, and, when the oper
ating temperature is approached, hydrocarbon
~ ?uid is admitted through inlet 14. The ?nished
gas is allowed to pass out through pipe G.
In the operation of the apparatus as described,
the incoming gases to be treated, such as propane
or butane, or mixtures of these, enter through
pipe M in liquid or gaseous form. Ordinarily,
they will pass through heater A where they will
be heated by the combustion gases.
After being heated by the heat exchanger A,
the hydrocarbons pass by point A’, where the
gases are mixed with a controlled quantity of
steam. This mixture is led into catalytic tubes
or chambers.
The reaction is extremely endothermic, re
quiring the addition of large quantities of heat to
the reaction chambers. Since the reaction is
strongly endothermic, the heat withdrawn at the
catalyst lowers the temperature to such a degree
that the reaction ceases when conversion is only
partly complete. This can be prevented by intro
(55 ducing additional heat into the catalyst or by
preheating the gases to an impractically high
temperature. We have discovered that the use
of excessive preheat temperatures can also be
avoided by a method for which the catalyst tube
shown in Fig. 3 is used. The gaseous mixture, to
undergo conversion, is heated above minimum re
action temperature to only a fraction of the ex~
tent necessary to subsequently cause complete
reaction, after which on passing through a por
tion of the catalyst bed, a partial reaction takes
place, the temperature falling to a minimum re
action temperature. The gas mixture, after un
dergoing partial conversion in this manner, must
be heated to undergo a further partial conver
sion. Additional partial conversions may be sub
sequently applied until the desired reduction in
calori?c value is obtained.
The process in the apparatus may be conducted
at about 650° to 800° C., but best results are ob
tained in most cases within a range of 700°~750° 10
C. We have found such temperatures can be
maintained easily if the catalyst is divided into
several portions which are so arranged that the
reacting gases pass through them in parallel re
lation or successively. The catalyst segments in 15
Fig. 3 are connected in the furnace by a piece of
tubing of sufficient length so that the heat to be
used in the reaction is taken up by radiation and
conduction from the furnace. By regulating the
furnace temperature, the heat loss due to the 20
endothermic nature of the reaction may be com
pensated by the connecting tubes, and the tem
perature of all the catalyst bodies kept high
enough to permit reaction.
After the mixture has reacted to the desired
degree in the catalytic chambers, it passes out
through pipe E’ to heat exchanger ! l to heat the
incoming water and from there the reacted gas
passes through pipe G where it may be diluted
by ?ue gases. If desired, it may be diluted by 30
air, combustion products, or other diluent gases,
or enriched with hydrocarbons, depending on the
calori?c value and density desired. The ?nished
product leaves pipe G to the necessary source for
use as fuel gas.
It may be desired to divert the hydrocarbons
directly into the catalytic chambers. In this
event, the valves in branch pipes J’, J2, J 3, J 4 and
J 5, (Fig. 3), are partially opened, and the hydro
carbons pass directly into the catalytic cham 40
This will avoid excessive cracking prior
to catalytic conversion when the more unstable
hydrocarbons are treated. Air may be intro
duced to supply heat to the several catalyst
chambers alone or in admixture with hydrocar 45
The combustion gases, assisted by radiation
from ba?ie 4a, function to maintain the tempera
ture of the reacting mixture ?owing through the
catalytic chambers, and from there pass up into 50
the stack In.
As example of the application of the process
to be conducted in the apparatus, the following
data are cited. In practicing the invention, an
apparatus essentially of the type shown in Figs.
1 and 2 was used. The catalyst consisted of 150
square feet of nickel screen in strips 12 feet long
and 16 inches wide, folded longitudinally to per
mit their introduction into chromium alloy steel
tubes C’, C2, C3, C4 of about 31/2 inches in in 60
ternal diameter. The tubes were disposed in
the furnace which maintained in the tubes the
average temperature shown in the following table
in the neighborhood of the catalyst. A mixture
of steam and butane was passed at a uniform 65
rate through the tubes wherein conversion into
gas of lower speci?c gravity and calori?c value
was produced.
The catalyst screen was activat
ed before practicing the process by heating the
screen three hours in air at 800° C. The oxi
dized surface was then reduced to a rough but
tenacious coating by reducing with hydrogen at
400° C., after which a strong aqueous solution
of nickel and aluminum nitrates in the molecular
ratio of 1 to 2 was applied. A clean gas, free
from tar, was produced continuously over a long
period without the formation of carbon.
The following shows the results:
What we claim and desire to secure by Letters
Patent is:
1. Gas
adapted for use in connection with highly en
Temperature degrees centigrade _______ _.
Butane-pubic feet per hour _____ _.
Steam-pounds per hour ________ __
Finished gas-cubic feet per hour
Finished gas—speci?c gravity____.
Finished gas B. t. u. per cubic foot
Finished gas analysis:
Carbon dioxide ____________________ “
Carbon monoxide _____ __
dothermic catalytic gas producingrreactions, said
apparatus comprising a combustion chamber,
a radiant heating chamber adjacent to but sepa
rated from said combustion chamber, a reaction
tube extending through said radiant heating
chamber, said tube comprising spaced catalyst
containing chambers and intermediate connect
ing conduits, said conduits being of such length
as to enable the reaction mixture passing there
through between catalyst chambers to ‘absorb
Propane _______ __
Both increased ?ow rate and decreased cata
lyst temperature decrease the extent of con
version to give a resultant increase in calori?c
20 value. The properties of the gas may also be
modi?ed by the admixing of other gases.
In case it is desired to decrease the calori?c
value and increase the speci?c gravity of the
combustion gases, or other suitable
suf?cient heat from said radiant heating cham
ber to enable the reaction to proceed, in part at
least, in said chambers, whereby excessive pre
heat temperatures of said reaction mixture may
be avoided, and additional means for selectively
controlling the temperature of said mixture in
said conduits.
2. Gas
adapted for use in connection with the endo
thermic generation of gas, said apparatus com
diluent gases can be added after the gases come
prising a source of heat, a reaction tube in in
out of the reaction chamber. In case it is de
sired to have a gas of very high calori?c value
and comparatively 10W gravity, hydrocarbon can
be added through H5 to the ?nished gas after
direct heat exchange relationship with said source
of heat, said tube comprising a plurality of spaced
reaction chambers and intermediate connecting
portions, whereby the reaction mixture is adapt
ed to pass through said chambers in succession, 30
said connecting portions being of such length as
to enable the reaction mixture passing there
through to absorb su?icient heat from said heat
source to enable the gas generation to proceed,
in part at least, in said reaction chambers, and 35
means for introducing hydrocarbons and the like
into said mixture progressively as it passes through
the apparatus.
it leaves the reaction chamber. Simpler paraf
?ns may also be added through 95 to the hot gas
leaving the catalyst. This would e?ect consid
erable cracking of the hydrocarbon, and also a
large increase in volume.
From the foregoing it is believed that the con
struction, operation and advantages of our im
proved apparatus may be readily understood by
those skilled in the art, and it is apparent that
changes may be made in the details disclosed,
without departing from the spirit of the inven
tion, as expressed in the claims.
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